Acetylated Derivatives of Castor Oil and Their Blends with Epoxidized Fatty Acid Esters

ABSTRACT

The present disclosure is directed to acetylated castor components and compositions including the same. The acetylated castor component may be an acetylated castor oil and/or an acetylated castor wax. The acetylated castor component may be blended with an epoxidized fatty acid ester. The present acetylated castor components and blends find advantageous application as a plasticizer.

PRIORITY

This application is a continuation of U.S. patent application Ser. No.13/498,745, filed on Mar. 28, 2012; which is a 371 U.S. National Phaseentry of International Application No. PCT/US2010/050676, filed on Sep.29, 2010; which claims the benefit of U.S. Provisional PatentApplication No. 61/247,383, filed on Sep. 30, 2009; the entire contentsof all are incorporated by reference herein.

BACKGROUND

Plasticizers are compounds or mixtures of compounds that are added topolymer resins to impart softness and flexibility. Phthalic aciddiesters (also known as “phthalates”) are known plasticizers in manyflexible polymer products, such as polymer products formed frompolyvinyl chloride (PVC) and other vinyl polymers. Examples of commonphthalate plasticizers include di-isononyl phthalate (DINP), diallylphthalate (DAP), di-2-ethylhexyl-phthalate (DEHP), dioctyl phthalate(DOP) and diisodecyl phthalate (DIDP). Other common plasticizers, usedfor high temperature applications, are trimellitates and adipicpolyesters. Mixtures of plasticizers are often used to obtain optimumproperties.

Phthalate plasticizers have recently come under intense scrutiny bypublic interest groups that are concerned about the negativeenvironmental impact of phthalates and potential adverse health effectsin humans (especially children) exposed to phthalates.

Consequently, a need exists for phthalate-free plasticizers for polymerresins. A need further exists for phthalate-free plasticized polymersthat have the same, or substantially the same, chemical, mechanical,and/or physical properties as polymers containing phthalateplasticizers.

SUMMARY

The present disclosure is directed to acetylated castor components andcompositions composed of the same. A nonlimiting beneficial applicationfor the present acetylated castor components is as a plasticizer.

In an embodiment, an acetylated castor oil is provided. The acetylatedcastor oil has a hydroxyl number from 0 to less than 5 as measured inaccordance with DIN 53402.

In an embodiment, an acetylated castor wax is provided. The acetylatedcastor wax has a viscosity less than 2000 m Pa s as measured inaccordance with ASTM D445 at 25° C.

The present disclosure provides a composition. The composition mayinclude one, two, three, or more plasticizers. In an embodiment, thecomposition comprises a first plasticizer and a second plasticizer. Thefirst plasticizer includes the acetylated castor component. The secondplasticizer includes one or more other plasticizers including, but notlimited to, an epoxidized fatty acid ester. The acetylated castorcomponent can be an acetylated castor oil, an acetylated castor wax, andcombinations thereof.

In an embodiment, a polymeric composition is provided. The polymericcomposition comprises a polymeric resin and a plasticizer compositioncontaining one, two, three, or more plasticizers. The plasticizercomposition comprises an acetylated castor component and optionally oneor more other plasticizers including, but not limited to, an epoxidizedfatty acid ester.

In an embodiment, a coated conductor is provided. The coated conductorcomprises a conductor and a coating on the metal conductor. The coatingcomprises a polymeric resin and a plasticizer composition containingone, two, three, or more plasticizers. The plasticizer includes a firstplasticizer and optionally a second plasticizer. The first plasticizerincludes the acetylated castor component. The second plasticizercontains one or more other plasticizers including, but not limited to,an epoxidized fatty acid ester.

An advantage of the present disclosure is an environmentally safeplasticizer for polymer resins.

An advantage of the present disclosure is a phthalate-free plasticizerwith low, or no, adverse health risk to humans.

An advantage of the present disclosure is a phthalate-free plasticizerwhich provides the same, or substantially the same, properties to apolymer resin as the same polymer resin containing aphthalate-containing plasticizer.

An advantage of the present disclosure is a coating for wire and cablethat is phthalate-free.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot showing the shear dependent viscosity for a comparativesample and a composition in accordance with an embodiment of the presentdisclosure.

DETAILED DESCRIPTION

The present disclosure is directed to acetylated castor components andcompositions including the same. The compositions provided herein aresuitable for use as plasticizers in polymer resins and vinyl chlorideresins in particular.

All references to the Periodic Table of the Elements refer to thePeriodic Table of the Elements published and copyrighted by CRC Press,Inc., 2003. Also, any references to a Group or Groups shall be to theGroup or Groups reflected in this Periodic Table of the Elements usingthe IUPAC system for numbering groups. Unless stated to the contrary,implicit from the context, or customary in the art, all parts andpercents are based on weight and all test methods are current as of thefiling date of this disclosure. For purposes of United States patentpractice, the contents of any referenced patent, patent application orpublication are incorporated by reference in their entirety (or itsequivalent U.S. version is so incorporated by reference) especially withrespect to the disclosure of synthetic techniques, product andprocessing designs, polymers, catalysts, definitions (to the extent notinconsistent with any definitions specifically provided in thisdisclosure), and general knowledge in the art.

The numerical ranges in this disclosure are approximate, and thus mayinclude values outside of the range unless otherwise indicated.Numerical ranges include all values from and including the lower and theupper values, in increments of one unit, provided that there is aseparation of at least two units between any lower value and any highervalue. As an example, if a compositional, physical or other property,such as, for example, molecular weight, melt index, etc., is from 100 to1,000, then the intent is that all individual values, such as 100, 101,102, etc., and sub ranges, such as 100 to 144, 155 to 170, 197 to 200,etc., are expressly enumerated. For ranges containing values which areless than one or containing fractional numbers greater than one (e.g.,1.1, 1.5, etc.), one unit is considered to be 0.0001, 0.001, 0.01 or0.1, as appropriate. For ranges containing single digit numbers lessthan ten (e.g., 1 to 5), one unit is typically considered to be 0.1.These are only examples of what is specifically intended, and allpossible combinations of numerical values between the lowest value andthe highest value enumerated, are to be considered to be expresslystated in this disclosure. Numerical ranges are provided within thisdisclosure for, among other things, the amounts for components in thecomposition and/or coating, additives, and various other components inthe composition, and the various characteristics and properties by whichthese components are defined.

As used with respect to a chemical compound, unless specificallyindicated otherwise, the singular includes all isomeric forms and viceversa (for example, “hexane”, includes all isomers of hexaneindividually or collectively). The terms “compound” and “complex” areused interchangeably to refer to organic-, inorganic- and organometalliccompounds. The term, “atom” refers to the smallest constituent of anelement regardless of ionic state, that is, whether or not the samebears a charge or partial charge or is bonded to another atom. The term“amorphous” refers to a polymer lacking a crystalline melting point asdetermined by differential scanning calorimetry (DSC) or equivalenttechnique.

The terms “comprising”, “including”, “having” and their derivatives arenot intended to exclude the presence of any additional component, stepor procedure, whether or not the same is specifically disclosed. Inorder to avoid any doubt, all compositions claimed through use of theterm “comprising” may include any additional additive, adjuvant, orcompound whether polymeric or otherwise, unless stated to the contrary.In contrast, the term, “consisting essentially of” excludes from thescope of any succeeding recitation any other component, step orprocedure, excepting those that are not essential to operability. Theterm “consisting of” excludes any component, step or procedure notspecifically delineated or listed. The term “or”, unless statedotherwise, refers to the listed members individually as well as in anycombination.

“Composition” and like terms mean a mixture or blend of two or morecomponents.

“Blend,” “polymer blend” and like terms mean a blend of two or morepolymers, as well as blends of polymers with various additives. Such ablend may or may not be miscible. Such a blend may or may not be phaseseparated. Such a blend may or may not contain one or more domainconfigurations, as determined from transmission electron spectroscopy,light scattering, x-ray scattering, and any other method known in theart.

The term “polymer” (and like terms) is a macromolecular compoundprepared by reacting (i.e., polymerizing) monomers of the same ordifferent type. “Polymer” includes homopolymers and copolymers.

In an embodiment, the compositions disclosed herein are phthalate-free.The term “phthalate-free composition,” as used herein, is a compositiondevoid of phthalate or is otherwise free of phthalate. A “phthalate,” isa compound which includes the following structure (I):

wherein R and R′ may be the same or different. Each of R and R′ isselected from a substituted-/unsubstituted-hydrocarbyl group having 1 to20 carbon atoms. As used herein, the term “hydrocarbyl” and“hydrocarbon” refer to substituents containing only hydrogen and carbonatoms, including branched or unbranched, saturated or unsaturated,cyclic, polycyclic, fused, or acyclic species, and combinations thereof.Nonlimiting examples of hydrocarbyl groups include alkyl-, cycloalkyl-,alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, aralkyl,alkylaryl, and alkynyl-groups. Each position 3, 4, 5, and 6 may bepopulated by hydrogen or other moiety.

In an embodiment, an acetylated castor component is provided. A “castorcomponent,” as used herein, is a castor oil, a castor wax, or a mixturethereof. The term “castor oil” is a pale yellow-to-colorless viscousliquid obtained from the castor bean/seed of the castor plant Ricinuscommunis. Castor oil is a triglyceride in which from about 85 wt % toabout 95 wt % of the fatty acid chains are ricinoleic acid. A “fattyacid,” as used herein, is a monocarboxylic acid composed of an aliphaticchain containing 4 to 22 carbon atoms with a terminal carboxyl group(COOH). The fatty acid can be saturated or unsaturated, branched orunbranched, and may or may not include one or more hydroxyl group(s).

A nonlimiting compositional representation of castor oil is provided atRepresentation (II) below.

Compositional Representation of Castor Oil (II)

Wt % based on total weight of the castor oil

The term “castor wax” is hydrogenated castor oil, and is a hard,brittle, high melting point wax with about 40 wt % to about 95 wt %glyceryl trihydroxystearate. It is produced by the hydrogenation ofcastor oil, typically in the presence of a nickel catalyst. Castor waxis odorless and is insoluble in water. Castor wax may be partially orfully hydrogenated castor oil.

The castor component is acetylated. The term “acetylating” or“acetylation,” as used herein, is the process of introducing an acetylgroup into the molecule of a compound having —OH groups. In other words,acetylation replaces H of the —OH groups with CH₃CO— groups. Acetylationmay also occur with a fatty acid moiety having a hydroxyl group (i.e.,the —OH group at C₁₂ of the ricinoleic acid moiety of a glyceride).Nonlimiting examples of suitable acetylation reagents include aceticanhydride and acetyl chloride. Thus, an “acetylated castor component”(or “ACC”) is a castor component that has been subjected to anacetylation reaction. In particular, the acetylated castor component maybe an acetylated castor oil (“ACO”) or an acetylated castor wax (“ACW”)or mixtures thereof. The ACW may be fully or partially hydrogenated.Nonlimiting examples of ACO and ACW are Flexricin® P-8 (product ofVertellus) and Paricin® 8 (product of Vertellus), respectively.

Some, substantially all, or all, of the —OH groups of the castorcomponent may be acetylated. The acetylation results in an acetylatedcastor component having a lower hydroxyl number than the castorcomponent, including from 0 to less than 15, or from 0 to less than 10,or from 0 to less than 5, or 0 to less than 2, or 0.

In an embodiment, the castor component is composed solely of glyceryltrihydroxystearate. Consequently, the ACC may be acetylated glyceryltrihydroxystearate.

In one embodiment, the acetylated glyceryl trihydroxystearate has ahydroxyl number from 0 to less than 15, or from 0 to less than 10, orfrom 0 to less than 5, or from 0 to less than 2, or 0. In anotherembodiment, the acetylated glyceryl trihydroxystearate has a viscosityfrom about 100 mPa s to less than about 2000 mPa s at 25° C.

Nonlimiting properties for the castor components and nonlimitingembodiments of the present acetylated castor component are provided inTable 1 below.

TABLE 1 Acetylated Castor Acetylated Castor Properties Castor Oil Oil(ACO) Castor Wax Wax (ACW) Melting Point (° C.) Liq @ RT Liq @ RT 60-87Liq @ RT Density (g/cc) 0.945-0.965 0.950-0.960 solid 0.950-0.960 at 25°C. Acid number <3 1-8  <3 1-8 (mg KOH/g) Iodine value (gI₂/100 g) 82-90≧40 <45 <40 Hydroxyl Number (mg 150-175 0 to less than 5  150-175 0 toless than 15 KOH/g) Viscosity mPas (@ 25 C.) 600-900 50 to less than1000 100 to less than 2000

Applicants have surprisingly discovered that reduced viscosity of theacetylated castor component results in improved plasticizercompositions.

Complete, or substantially complete, acetylation of the ACC yields aliquid plasticizer composition with a viscosity suitable for use withpolymeric resins and vinyl chloride resins in particular. In anembodiment, Applicants have surprisingly discovered a liquid ACW with aviscosity from about 100 mPa s to less than about 2000 mPa s at 25° C.

In another embodiment, the ACW has a hydroxyl number from 0 to less than15. In a further embodiment, the ACW may also have an iodine number of 0to less than 40 g I₂/100 g.

Applicants also have discovered a liquid ACO with a hydroxyl number from0 to less than 5 which has a viscosity from about 50 mPa s to less than1000 mPa s at 25° C. The ACO may also have an iodine number from about40 g I₂/100 g to about 90 g I₂/100 g.

In an embodiment, the acetylated castor component has an acid numberfrom about 0 mg KOH/g to about 8 mg KOH/g.

In an embodiment, the acetylated castor component has an APHA color fromabout 0 to about 3000, or from about 0 to about 1000, or from about 0 toabout 500.

The grade of castor oil or castor wax used for acetylation has an effecton the color of the ACC, as well as the amount of insolubles formed attemperatures below 40° C. In general, the lower the temperature, themore insolubles are formed. Different grades of castor oil or castor waxcan result in significantly different color and amount of insolubles,even when the conditions during acetylation are identical.

Any known grade of castor oil can be used to make the ACC (or thehydrogenated castor oil that is used to make the ACC) including, but notlimited to, Commercial Grade/Industrial Grade Castor Oil (produced bycrushing steam cooked castor seeds in expeller and filtering thecollected oil to remove physical impurities); First Special GradeRefined Castor Oil (produced by bleaching Commercial Grade Castor Oil,using bleaching earth and activated carbon to reduce colour, free fattyacid content and moisture content, and filtration); Pale Pressed GradeRefined Castor Oil (a premium product produced from the first pressingof the castor seed that is pale yellow viscous liquid in appearance andfree from suspended matter, light in colour and low in acidity); PharmaGrade Castor Oil (produced by first pressing of castor seed, withoutlosing medicinal qualities); Cold Pressed Castor Oil (pure virgintransparent castor oil extracted in its natural form by pressing seedswithout using steam cooking); and Dehydrated Castor Oil; and BlownCastor Oil (produced by oxidizing castor oil under thermally controlledcondition). The foregoing grades of castor oil are available from KelothOleochem Pvt., Ltd., Gujarat, India.

In an embodiment, the castor wax is recrystallized from solvents such asethyl acetate or acetone before use in the acetylation reaction.Re-crystallization of castor wax results in an ACC product that isdesirably lighter in color and which can also have desirably lessinsoluble components.

Applicants have surprisingly and unexpectedly discovered an acetylatedcastor component with (i) a low hydroxyl number, (ii) a low viscosity,and optionally (iii) a low iodine number which yields a plasticizer withexcellent compatibility when added to polymeric resins (and vinylchloride resins in particular). The present ACC is phthalate-free andprovides a plasticizer that replicates all, or substantially all, theproperties afforded by phthalate-based plasticizers.

The acetylated castor component may comprise two or more embodimentsdisclosed herein.

The present disclosure provides a composition that may include one, two,three, or more plasticizers. In an embodiment, a composition is providedand includes a first plasticizer and a second plasticizer. The firstplasticizer includes the ACC. The second plasticizer includes one ormore other plasticizer. In an embodiment, the composition includes ablend of (i) the ACC (first plasticizer) and (ii) one or more epoxidizedfatty acid ester (EFA) (second plasticizer). The ACC may be any ACC(i.e., any ACO, any ACW, and combinations thereof) as disclosed abovewith no limit regarding hydroxyl number and/or viscosity. The term“epoxidized fatty acid ester,” as used herein, is a compound with atleast one fatty acid moiety which contains at least one epoxide group.An “epoxide group” is a three-membered cyclic ether (also called oxiraneor an alkylene oxide) in which an oxygen atom is joined to each of twocarbon atoms that are already bonded to each other. Nonlimiting examplesof suitable epoxidized fatty acid esters include epoxidized animal andvegetable oils, such as naturally occurring epoxidized oils, epoxidizedsoybean oil (ESO), epoxidized propylene glycol dioleate, epoxidized cornoil, epoxidized sunflower oil, epoxidized palm oil, epoxidized linseedoil, epoxidized canola oil, epoxidized rapeseed oil, epoxidizedsafflower oil, epoxidized tall oil, epoxidized tung oil, epoxidized fishoil, epoxidized beef tallow oil, epoxidized castor oil, epoxidizedmethyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexylstearate, epoxidized stearyl stearate,3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate epoxidizedsoybean oil, epoxidized fatty acid methyl esters, epoxidized derivativesof each of the foregoing, and any combination of the foregoing. Anonlimiting example of naturally occurring epoxidized oil is Vernoniaoil.

The second plasticizer may also include epoxidized polybutadiene,tris(epoxypropyl)isocyanurate, bisphenol A diglycidyl ether,vinylcyclohexene diepoxide, dicyclohexene diepoxide, and any combinationthereof.

The epoxidized fatty acid ester can be prepared in a variety of ways.For example, natural oils can be used as the starting material. In thisinstance, the natural oils may be saponified to the fatty acids and thenesterified with alcohols. Next, the low molecular weight esters areepoxidized. The unsaturated ester can be epoxidized with a per-acid.

Alternatively, a glycidyl ester of the fatty acid can be prepared viaepichlorohydrin or related chemicals. In yet another alternate, it ispossible to transesterify the triglyceride with alcohols and thenepoxidize the unsaturated fatty ester with a per-acid.

In an embodiment, the epoxidized fatty acid ester can be any epoxidizedfatty acid C₁-C₁₄ ester, including methyl, ethyl, propyl, butyl, and2-ethylhexyl esters. In a further embodiment, the epoxidized fatty acidester is an epoxide of a fatty acid methyl ester.

A nonlimiting example for the preparation of an epoxide of a fatty acidmethyl ester begins with soy oil, wherein the soy oil is transesterifiedwith methanol to make the methyl ester of the fatty acids in the oil.Glycerol is removed from the reaction products due to insolubility. Asolution of per-acetic acid in ethyl acetate is used to epoxidize thedouble bonds on the fatty acids. The per-acid is kept below 35% per-acidand 35 degrees Celsius to prevent detonation. After completion, theethyl acetate and product acetic acid are removed via vacuum stripping.

In an embodiment, the epoxidized fatty acid ester is epoxidized soybeanoil.

The ACC/EFA mixture may be referred to as a “ACC/EFA plasticizer.” TheACC/EFA plasticizer may include from about 1 wt % to about 99 wt % ACCand from about 99 wt % to about 1 wt % EFA, or from about 30 wt % toabout 99 wt % ACC and from about 70 wt % to about 1 wt % EFA (based onthe total weight of the plasticizer composition). In an embodiment, theACC/EFA plasticizer contains less than 70 wt % ACC. Weight percent isbased on total weight of the ACC/EFA plasticizer.

A “plasticizer composition” or “plasticizer” is a substance that lowersthe modulus and tensile strength, and increases flexibility, elongation,impact strength, and tear strength of the polymeric resin (typically athermoplastic polymer) to which it is added. A plasticizer may alsolower the melting point of the polymeric resin, which lowers the glasstransition temperature and enhances processability of the polymericresin to which it is added.

In an embodiment, the plasticizer composition includes an ACW with aviscosity from about 100 mPa s to about 2000 mPa s at 25° C. The ACW mayalso have a hydroxyl number from 0 to less than 15, or 0 to less than10, or 0 to less than 5, or 0 to less than 2, or 0. The ACW is blendedwith any of the foregoing EFAs.

In an embodiment, the plasticizer composition includes an ACO with ahydroxyl number from 0 to less than 15, or from 0 to less than 10, orfrom 0 to less than 5, or 0. The ACO may also have a viscosity from 50mPa s to less than 1000 mPa s at 25° C. The ACO is blended with any ofthe foregoing EFAs.

The plasticizer composition may include one or more ACCs and/or one ormore EFAs. In an embodiment, the plasticizer composition includes anacetylated castor component having a hydroxyl number from 0 to less than15, or from 0 to less than 10, or from 0 to less than 5, or from 0 toless than 2, or 0, and epoxidized soybean oil (ESO). In a furtherembodiment, the ACC of the plasticizer composition has a hydroxyl numberof 0 and the plasticizer composition also includes ESO.

In an embodiment, the plasticizer composition includes an ACC, a firstEFA, and a second EFA. The second EFA is different than the first EFA.In a further embodiment, the plasticizer composition includes an ACC,ESO, and an epoxidized propylene glycol dioleate. In yet anotherembodiment, the plasticizer composition includes an ACC, ESO, and anepoxidized fatty acid methyl ester.

Although the plasticizer composition of this disclosure may bephthalate-free, in an embodiment, the plasticizer composition may alsocomprise other plasticizers including, but not limited to, phthalates(such as di-isononyl phthalate, diallyl phthalate,di-2-ethylhexyl-phthalate, dioctyl phthalate, diisodecyl phthalate anddiisotridecyl phthlate), trimellitates (such as trioctyl trimellitate,triisononyl trimellitate and triisodecyl trimellitate), citrates,Grindsted® Soft-N-Safe acetylated monoglyceride of hydrogenated castoroil (product of Danisco), Hexamoll® DINCH diisononyl ester of1,2-Cyclohexanedicarboxylic acid (product of BASF), benzoates and adipicpolyesters.

The present plasticizer composition may comprise two or more embodimentsdisclosed herein.

The present composition composed of ACC alone or in combination with anyEFA or other plasticizers may be used in a variety of compositions orproducts. Nonlimiting examples of suitable applications for thecomposition include cosmetic compositions/products, foodcompositions/products, and polymeric compositions/products, softthermoplastic polyolefins, profiles (gaskets), films, etc.

The present disclosure provides a polymeric composition. In anembodiment, a polymeric composition is provided which includes apolymeric resin and the present plasticizer composition containing one,two, three, or more plasticizers. The plasticizer composition may be anyACC alone or in combination with any EFA or other plasticizer asdisclosed herein. The polymeric composition contains from about 1 wt %to about 99 wt % of the polymeric resin and from about 99 wt % to about1 wt % of the plasticizer composition. Weight percent is based on totalweight of the polymeric composition.

Nonlimiting examples of suitable polymeric resins include polysulfides,polyurethanes, acrylics, epichlorohydrins, nitrile rubber,chlorosulfonated polyethylene, chlorinated polyethylene,polychloroprene, styrene butadiene rubber, natural rubber, syntheticrubber, EPDM rubber, propylene-based polymers, ethylene-based polymers,and vinyl chloride resins. The term, “propylene-based polymer,” as usedherein, is a polymer that comprises a majority weight percentpolymerized propylene monomer (based on the total amount ofpolymerizable monomers), and optionally may comprise at least onepolymerized comonomer. The term, “ethylene-based polymer,” as usedherein, is a polymer that comprises a majority weight percentpolymerized ethylene monomer (based on the total weight of polymerizablemonomers), and optionally may comprise at least one polymerizedcomonomer.

The term “vinyl chloride resin,” as used herein, is a vinyl chloridepolymer, such as polyvinyl chloride (PVC), or a vinyl chloride copolymersuch as vinyl chloride/vinyl acetate copolymer, vinylchloride/vinylidene chloride copolymer, vinyl chloride/ethylenecopolymer or a copolymer prepared by grafting vinyl chloride ontoethylene/vinyl acetate copolymer. The resin composition can also includea polymer blend of the above-mentioned vinyl chloride polymer or vinylchloride copolymer with other miscible or compatible polymers including,but not limited to, chlorinated polyethylene, thermoplasticpolyurethane, olefin polymers such as a methacryl polymer oracrylonitrile-butadiene-styrene polymer (ABS resin).

In an embodiment, the vinyl chloride resin is polyvinyl chloride (PVC).

In an embodiment, the polymeric composition is a thermoplasticcomposition. A “thermoplastic composition,” as used herein, is apolymeric composition (1) that has the ability to be stretched beyondits original length and retract to substantially its original lengthwhen released and (2) softens when exposed to heat and returns tosubstantially its original condition when cooled to room temperature.

In an embodiment, the polymeric composition includes the polymeric resinand a plasticizer including one or more ACC, optionally one or more EFA,and optionally a second EFA.

In an embodiment, the polymeric composition includes PVC, an ACC andoptionally an EFA. The composition has a Shore hardness from about A60to about A100, or from about A70 to about A95. In an embodiment, thepolymeric composition has a Shore hardness from about D10 to about D70,or from about D20 to about D60.

In an embodiment, the plasticizer composition has a solution temperaturefrom about 140° C. to about 200° C. as measured in accordance with DIN53408. Applicants have surprisingly discovered that the plasticizercomposition composed of ACC and an EFA unexpectedly provides aplasticizer with low viscosity and low volatility, which is particularlysuitable for high temperature wire and cable applications, and whichdoes not migrate out of a thermoplastic polymer in which it isincorporated. In addition, the solution temperature (of 140° C.-200° C.)for the present plasticizer composition is similar to the solutiontemperature of conventional high molecular weight plasticizers(typically between about 140° C. and about 180° C.). Moreover, theviscosity of the present plasticizer composition is less than theviscosity of conventional high molecular weight plasticizers, such asadipic polyester plasticizers. For example, adipic polyesterplasticizers, known commercially as Ultramoll® IV and Ultramoll® IIIadipic polyesters (products of Lanxess) have very high viscosity(approximately 6000 to 6500 mPa s at 25° C.). It is known that the lowerthe viscosity of a plasticizer, the faster is its uptake into PVCpowder. Hence, the present plasticizer compositions are absorbed intoPVC at a faster rate than adipic polyester plasticizers, and eventrimellitates of lower or similar viscosity. The present plasticizercomposition exhibits an unexpected synergy between low viscosity andhigh molecular weight and yields a phthalate-free, safe, plasticized PVCwith physical, chemical, and mechanical properties that meet and/orexceed the properties of PVC resins plasticized with conventional adipicpolyester plasticizers or conventional phthalate-based plasticizers orconventional trimellitate-based plasticizers. Especially noteworthy isthe retention of tensile properties exhibited by the present compositionafter oven aging for 168 hours at temperatures as high as 136° C.

The present polymeric composition exhibits the same, or better,flexibility and/or elongation when compared to polymer resins containingconventional adipic polyester, phthalate, and/or trimellitateplasticizers. In an embodiment, the present polymeric composition is ablend of PVC and an ACC/EFA plasticizer and has a Shore hardness fromabout A60 to about A100, or from about A70 to about A95, or from aboutD10 to about D70, or from about D20 to about D60. Shore hardness ismeasured in accordance with ASTM D2240.

In an embodiment, the polymeric composition is a blend of PVC andACC/EFA plasticizer and has a glass transition temperature (“Tg”) fromabout 10° C. to about 90° C., or from about 20° C. to about 80° C., orfrom about 30° C. to about 75° C.

In an embodiment, the polymeric composition is composed of a blend ofPVC and the ACC/EFA plasticizer. The polymeric composition is moldedinto a plaque. The plaque has a tensile strength retention greater thanabout 70% after 168 hours heat aging at 113° C. as measured on dogbonescut from 30 mil thick plaques in accordance with ASTM D638.

In an embodiment, the polymeric composition is composed of a blend ofPVC and the ACC/EFA plasticizer. The polymeric composition is moldedinto a plaque. The plaque has a tensile strength retention greater thanabout 70% after 168 hours heat aging at 136° C. as measured on dogbonescut from 30 mil thick plaques in accordance with ASTM D638.

In an embodiment, the present polymeric composition is composed of ablend of PVC and the ACC/EFA plasticizer composition. The polymericcomposition is molded into a plaque. The plaque has a tensile elongationretention greater than about 30% after 168 hours heat aging at 113° C.as measured on 30 mil thick plaques in accordance with ASTM D638.

In an embodiment, the present polymeric composition is composed of ablend of PVC and the ACC/EFA plasticizer composition. The polymericcomposition is molded into a plaque. The plaque has a tensile elongationretention greater than about 30% after 168 hours heat aging at 136° C.as measured on 30 mil thick plaques in accordance with ASTM D638.

The tensile strength and tensile elongation is measured for (i) unagedand (ii) heat aged dogbone specimens cut from compression molded plaquesin accordance with ASTM D-638.

Any of the foregoing polymeric compositions may include one or more ofthe following additives: a filler, an antioxidant, a flame retardant(antimony trioxide, molybdic oxide and alumina hydrate), a heatstabilizer, an anti-drip agent, a colorant, a lubricant, a low molecularweight polyethylene, a hindered amine light stabilizer (having at leastone secondary or tertiary amine group) (“HALS”), UV light absorbers(such as o-hydroxyphenyltriazines), curing agents, boosters andretardants, processing aids, coupling agents, antistatic agents,nucleating agents, slip agents, viscosity control agents, tackifiers,anti-blocking agents, surfactants, extender oils, acid scavengers, metaldeactivators, and any combination thereof.

In an embodiment, the present polymeric composition includes a filler.Nonlimiting examples of suitable fillers include calcium carbonate,calcined clay, whiting, fuller's earth, magnesium silicate, bariumsulfate, calcium sulfate, strontium sulfate, titanium dioxide, magnesiumoxide, magnesium hydroxide, calcium hydroxide, hydrophilic fumed silica,hydrophobic (surface treated) fumed silica, and any combination of theforegoing. Nonlimiting examples of calcined clay are Satintone® SP-33and Polyfil® 70.

In an embodiment, the present polymeric composition includes anantioxidant. Nonlimiting examples of suitable antioxidants includehindered phenols such astetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydro-cinnamate)]methane;bis[(beta-(3,5-ditert-butyl-4-hydroxybenzyl)-methylcarboxyethyl)]sulphide,4,4′-thiobis(2-methyl-6-tert-butylphenol),4,4′-thiobis(2-tert-butyl-5-methylphenol),2,2′-thiobis(4-methyl-6-tert-butylphenol), and thiodiethylenebis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate; phosphites andphosphonites such as tris(2,4-di-tert-butylphenyl)phosphite anddi-tert-butylphenyl-phosphonite; thio compounds such asdilaurylthiodipropionate, dimyristylthiodipropionate, anddistearylthiodipropionate; various siloxanes; polymerized2,2,4-trimethyl-1,2-dihydroquinoline,n,n′-bis(1,4-dimethylpentyl-p-phenylenediamine), alkylateddiphenylamines, 4,4′-bis(alpha,alpha-dimethylbenzyl)diphenylamine,diphenyl-p-phenylenediamine, mixed di-aryl-p-phenylenediamines, andother hindered amine anti-degradants or stabilizers. Nonlimitingexamples of suitable antioxidants include Topanol® CA, Vanox® 1320,Irganox® 1010, Irganox® 245 and Irganox® 1076. The antioxidant orantioxidants may be added to the plasticizer composition of thisdisclosure. Antioxidants can be used in amounts of 0.01 to 5 wt % basedon the weight of the polymeric composition.

In an embodiment, the present polymeric composition includes a heatstabilizer. Nonlimiting examples of suitable heat stabilizers includelead-free mixed metal heat stabilizers, lead stabilizers, organic heatstabilizers, epoxides, salts of monocarboxylic acids, phenolicantioxidants, organic phosphites, hydrotalcites, zeolites, perchloratesand/or betadiketones. Nonlimiting examples of suitable betadiketones aredibenzoylmethane, palmitoyl benzoyl methane, stearoyl benzoyl methaneand mixtures thereof. A nonlimiting example of suitable dibenzoylmethaneis Rhodiastab® 83. A nonlimiting example of suitable mixtures ofpalmitoyl benzoyl methane and stearoyl benzoyl methane is Rhodiastab®50. Nonlimiting examples of suitable lead-free mixed metal heatstabilizers include Mark® 6797, Mark® 6776 ACM, Mark® 6777ACM,Therm-Chek® RC215P, Therm-Chek® 7208, Naftosafe® EH-314, Baeropan® MC90400 KA, Baeropan® MC 90400 KA/1, Baeropan® MC8553 KA-ST 3-US,Baeropan® MC 9238 KA-US, Baeropan® MC 90249 KA, and Baeropan® MC 9754KA. The heat stabilizer or heat stabilizers may be added to theplasticizer composition of this disclosure. Heat stabilizers can be usedin amounts of 0.1 to 10 wt % based on the total weight of the polymericcomposition.

In an embodiment, the present polymeric composition includes alubricant. Nonlimiting examples of suitable lubricants include stearicacid, metal salts of stearic acid, paraffin wax, and polyethyleneglycols. The lubricants may be used alone or in combination. Thelubricant may also be combined with the heat stabilizer.

In an embodiment, the present polymeric composition includes aprocessing aid. Nonlimiting examples of suitable processing aids includemetal salts of carboxylic acids such as zinc stearate or calciumstearate; fatty acids such as stearic acid, oleic acid, or erucic acid;fatty amides such as stearamide, oleamide, erucamide, or N,N′-ethylenebis-stearamide; polyethylene wax; oxidized polyethylene wax; polymers ofethylene oxide; copolymers of ethylene oxide and propylene oxide;vegetable waxes; petroleum waxes; non ionic surfactants; andpolysiloxanes. Processing aids can be used in amounts of 0.05 to 5 wt %based on the total weight of the polymeric composition.

The polymeric compositions are generally prepared according toconventional dry blend or wet blend methods known to those skilled inthe art of PVC compounding. The mixtures obtained from the blendingprocess can be further compounded with a mixer such as a Banbury batchmixer, a Farrel Continuous Mixer, or a single or twin screw extruder.

In an embodiment, the present polymeric composition is made byabsorption of the plasticizers of this disclosure in PVC powder to makea dry blend. Any suitable method/apparatus may be used to make the dryblend including, but not limited to, a Henschel mixer or a ribbonblender. The polymeric composition may contain other additives inaddition to the PVC and the plasticizer. The dry blend may then befurther compounded (via melt extrusion for example) and formed into anydesired shape (film, pellet, etc.).

With an optimal stabilizer and antioxidant package, the presentpolymeric compositions are suitable for applications requiring long termdry or wet insulation resistance testing at elevated temperatures, andother demanding applications where temperatures are as high as 136° C.

The present polymeric composition(s) may comprise two or moreembodiments disclosed herein.

The surprising properties of flexibility, low plasticizer volatility,low migration, low viscosity and/or high solution temperature exhibitedby the present polymeric composition make it well suited for wire andcable coating applications, and high temperature wire/cable applicationsin particular. Accordingly, the present disclosure provides a coatedconductor. A “conductor” is an element of elongated shape (wire, cable,fiber) for transferring energy at any voltage (DC, AC, or transient).The conductor is typically at least one metal wire or at least one metalcable (such as aluminum or copper) but may include optical fiber.

In an embodiment, a coated conductor is provided and includes aconductor and a coating on the conductor. The coating is composed of thepresent polymeric composition which includes the polymeric resin and thepresent plasticizer composition. The polymeric resin of the coating maybe any polymeric resin disclosed herein. The plasticizer composition maybe any plasticizer composition composed of one or more ACC alone orblended with one or more EFA, and/or blend with one or more otherplasticizers as disclosed herein.

A “metal conductor,” as used herein, is at least one metal wire and/orat least one metal cable. The coated metal conductor may be flexible,semi-rigid, or rigid. The coating (also referred to as a “jacket” or a“sheath” or “insulation”) is on the metal conductor or on anotherpolymeric layer around the conductor. The coating includes the presentcomposition. The composition may be any composition as disclosed herein.As used herein, “on” includes direct contact or indirect contact betweenthe coating and the metal conductor. “Direct contact” is a configurationwhereby the coating immediately contacts the metal conductor, with nointervening layer(s) and/or no intervening material(s) located betweenthe coating and the metal conductor. “Indirect contact” is aconfiguration whereby an intervening layer(s) and/or an interveningstructure(s) and/or intervening material(s) is/are located between themetal conductor and the coating. The coating may wholly or partiallycover or otherwise surround or encase the metal conductor. The coatingmay be the sole component surrounding the metal conductor.Alternatively, the coating may be one layer of a multilayer jacket orsheath encasing the metal conductor.

In an embodiment, the polymeric resin is a vinyl chloride resin such asPVC as discussed above. The PVC is blended with the plasticizercomposition to form the coating. The coating may include additionalcomponents. In an embodiment, the coating includes from about 1 wt % toabout 99 wt % or from about 20 wt % to about 80 wt %, or from about 30wt % to about 70 wt % PVC and from 99 wt % to about 1 wt %, or fromabout 80 wt % to about 20 wt %, or from about 70 wt % to about 30 wt %plasticizer composition. In a further embodiment, the coating containsfrom about 30 wt % to about 90 wt % PVC and from about 70 wt % to about10 wt % of the plasticizer composition.

The plasticizer composition may be any plasticizer composition disclosedherein. In an embodiment, the ACC present in the coating has a hydroxylnumber from 0 to less than 15, or from 0 to less than 10, or from 0 toless than 5, or from 0 to less than 5, or 0.

The coating may have any of the properties as discussed above for thepresent composition. In an embodiment, the coated conductor passes theheat test as measured in accordance with UL-1581. In another embodiment,the plasticizer composition in the coating has a solution temperaturefrom about 140° C. to about 200° C. In another embodiment, the coatinghas a Shore hardness from about A60 to about A100 as measured inaccordance with ASTM D2240. In another embodiment, the coating has aShore hardness from about D10 to about D70 as measured in accordancewith ASTM D 2240.

Nonlimiting examples of suitable coated metal conductors includeflexible wiring such as flexible wiring for consumer electronics, apower cable, a power charger wire for cell phones and/or computers,computer data cords, power cords, appliance wiring material, buildingwire, automotive wire, and consumer electronic accessory cords.

The present coated conductor may comprise two or more embodimentsdisclosed herein.

The coated conductor, such as a coated wire or a coated cable (with anoptional insulation layer), with a jacket comprising the compositiondisclosed herein can be prepared with various types of extruders, e.g.,single or twin screw types. A description of a conventional extruder canbe found in U.S. Pat. No. 4,857,600. An example of co-extrusion and anextruder can be found in U.S. Pat. No. 5,575,965. A typical extruder hasa hopper at its upstream end and a die at its downstream end. The hopperfeeds into a barrel, which contains a screw. At the downstream end,between the end of the screw and the die, there is a screen pack and abreaker plate. The screw portion of the extruder is considered to bedivided up into three sections, the feed section, the compressionsection, and the metering section, and two zones, the back heat zone andthe front heat zone, the sections and zones running from upstream todownstream. In the alternative, there can be multiple heating zones(more than two) along the axis running from upstream to downstream. Ifit has more than one barrel, the barrels are connected in series. Thelength to diameter ratio of each barrel is in the range of about 15:1 toabout 30:1.

The wire and cable constructions (i.e., a coated metal conductor) ofthis disclosure are made by extruding the present composition onto theconductor or onto the bundle of insulated conductors to form a coating(or a jacket) around the insulated conductors. The thickness of thejacket or insulation depends on the requirements of the desired end useapplication. Typical thickness of the jacket or insulation is from about0.010 inches to about 0.200 inches, or from about 0.015 inches to about0.050 inches. The present composition may be extruded into the jacketfrom previously made composition. Usually the present composition is inthe form of pellets for easy feeding into the extruder. The wire andcable jacket or insulation may be extruded directly from the compoundingextruder without going through the separate step of pelletizing thepresent composition. This one-step compounding/extrusion process wouldeliminate one heat history step for the composition.

A nylon layer may also be extruded over the insulation, such as inconventional THHN, THWN and THWN-2 constructions.

Nonlimiting examples of embodiments of the present disclosure areprovided below.

In an embodiment E1, an acetylated castor oil is provided having ahydroxyl number from 0 to less than 5 as measured in accordance with DIN53402. In an embodiment E2, an acetylated castor wax is provided havinga viscosity less than 2000 m Pa s as measured in accordance with ASTMD445 at 25° C.

In an embodiment E3, a composition comprises: an acetylated castorcomponent, and an epoxidized fatty acid ester. E4. The composition of E3wherein the acetylated castor component is selected from the groupconsisting of acetylated castor oil, acetylated castor wax, andcombinations thereof. E5. The composition of any of E3-E4 wherein theacetylated castor component has a hydroxyl number from 0 to less than15. E6. The composition of any of E3-E5 wherein the acetylated castorcomponent is an acetylated castor wax having a viscosity less than 2000mPa s at 25° C. as determined in accordance with ASTM D445. E7. Thecomposition of any of E3-E6 wherein the epoxidized fatty acid ester isselected from the group consisting of epoxidized soybean oil, epoxidizedpropylene glycol dioleate, epoxidized palm oil, epoxidized linseed oil,epoxidized fatty acid methyl esters, epoxidized derivatives of each ofthe foregoing, and combinations thereof. E8. The composition of any ofE3-E7 comprising from about 30 wt % to about 99 wt % acetylated castorcomponent and from about 1 wt % to about 70 wt % epoxidized fatty acidester. E9. The composition of any of claims E3-E8 comprising anacetylated castor component having a hydroxyl number from 0 to less than5; and epoxidized soybean oil. E10. The composition of any of claimsE3-E9 comprising a second epoxidized fatty acid ester.

In an embodiment E11, a polymeric composition comprises a polymericresin; and a plasticizer composition comprising an acetylated castorcomponent and optionally an epoxidized fatty acid ester. E12. Thecomposition of E11 comprising a composition of any of E1-E10. E13. Thecomposition of any of E 11-E12 wherein the polymeric resin comprises avinyl chloride resin. E14. The composition of any of E11-E13 wherein theplasticizer composition comprises a first epoxidized fatty acid esterand a second epoxidized fatty acid ester. E15. The composition of any ofE11-E14 wherein the composition is a plaque having a tensile elongationretention after 168 hours heat aging 113° C. of greater than 50%. E16.The composition of any of claims 11-15 wherein the composition is aplaque having a tensile elongation after 168 hours heat aging 136° C. ofgreater than 50%. E17. The composition of any of E11-E16 having a volumeresistivity from about 1.0E+10 to about 1.0E+17 Ohm cm.

In an embodiment E18, a coated conductor comprises: a conductor; andcoating on the conductor, the coating comprising a polymeric resin and aplasticizer composition comprising an acetylated castor component andoptionally an epoxidized fatty acid ester. E19. The coated conductor ofE18 wherein the coating comprises a composition of any of E1-E17. E20.The coated conductor of any of E18-E19 wherein coating passes the heattest as determined in accordance with UL-1581.

Test Methods

Acid number (or “acid value”) is a measure of the amount of free acidpresent in a compound. The acid number is the number of milligrams ofpotassium hydroxide required for the neutralization of free acid (fattyacid and/or other acid such as acetic acid, for example) present in onegram of a substance. The acid number is determined in accordance withGerman Standard DIN 53402 (mg KOH/g).

APHA color is measured using Color Quest XE colorimeter, available fromHunterLab, or equivalent; 20-mm transmission cell; HunterLab Universalsoftware, version 4.10 or equivalent; Black and White color referencetitles available from HunterLab, or equivalent; the measured APHA colorvalue of deionized (DI) water is zero.

Density at 25° C. is determined in accordance with German Standard DIN51 757 (g/cm³).

Dynamic storage modulus (G′) and Glass transition temperature (Tg) aredetermined by dynamic mechanical analysis (DMA) using a TA InstrumentAR1000N Rheometer having DMA fixtures. The specimen is in the form of arectangular solid and tested in tension mode. The temperature is variedfrom −100° C. to +160° C. at a ramp rate of 5° C./min, and the testfrequency is held constant at 6.283 rad/s (1 Hz). The storage and lossmodulus of the sample, as well as the tan delta, are measured as afunction of the temperature. The glass transition temperature (Tg) isdetermined from the peak tan delta measurement. Dynamic storage modulus(G′) at −20° C. is used as a measure of low temperature flexibility. Thestorage and loss modulus of viscoelastic materials are measures of thestored energy (representing the elastic portion) and the energydissipated as heat (representing the viscous portion).

Hydroxyl Number (or hydroxyl value) is an indication of the degree ofacetylation and is a measure of the number of hydroxyl groups present ina polymer. The hydroxyl number is the number of milligrams of potassiumhydroxide required to neutralize the hydroxyl groups in one gram ofpolymer. The hydroxyl number is determined in accordance with GermanStandard DIN 53 240 (mg KOH/g).

Iodine Number is an indication of the degree of hydrogenation and isdetermined in accordance with German Einheitsmethode DGF C-V 11a (53) (gI₂/100 g).

Plasticizer compatibility in the polymeric composition is assessed byvisual inspection of molded or extruded specimens aged at elevatedtemperatures (e.g., 113° C. or 136° C.) for defined lengths of time(e.g., 7 days). The extruded specimens may be in the form of a wire(i.e., insulation extruded over conductor). The amount of exudate (spew)on surface after 7 days at 113° C. or 136° C. is rated as “none”,“slight”, “moderate”, or “heavy”.

Shore hardness is determined in accordance with ASTM D 2240.

Solution Temperature is the temperature at which a heterogeneous mixtureof plasticizer and a PVC resin is observed to change to a single phase.Solution temperature is determined by immersing 1 gram PVC in 20 gramsof plasticizer and increasing the temperature stepwise until the PVC isseen to be completely dissolved by observation under a microscope, inaccordance with German Standard DIN 53 408 (° C.).

Surface smoothness of coated conductors (extruded wires) is measuredusing a surface roughness measuring apparatus made by Mitutoyo of Japan,in accordance with ANSI/ASME B46.1.

Temperature of 5% mass loss (° C.) is determined using TG/DTA 220. Theplasticizer specimen is heated from room temperature up to 600° C. at10K./min under inert gas purge, and the appearing mass loss and thermaleffects are recorded in thermograms. The higher the temperature for 5%mass loss, the lower the volatility.

Tensile strength (TS), tensile strength retention (TSR), tensileelongation (TE), and tensile elongation retention (TER) (at 2 inch/min)on unaged specimens, on specimens aged at 113° C. or at 136° C. for 168hours, is determined in accordance with ASTM D638 and UL 1581/2556either on dogbones cut from molded plaques or tubular insulationsremoved from coated conductors (extruded wires).

The term “UL 1581” is Underwriters Laboratories Reference Standard forElectrical Wires, Cables, and Flexible Cords. UL 1581 contains specificdetails for conductors, insulation, jackets and other coverings, and formethods of sample preparation, specimen selection and conditioning, andfor measurement and calculation that are required in wire and cablestandards.

Viscosity is determined in accordance with Standard ASTM D445,Brookfield-Viscosimeter at 25° C. and/or 40° C.

Volume resistivity (Ohm-cm) at 23° C. (Vol. Res.), with 500 volts directcurrent, is measured in accordance with ASTM D257. Specimens of 3.5 inchdiameter are cut from 40 mil thick molded plaques and tested using aHewlett Packard 16008A Resistivity Cell connected to a Hewlett Packard4329A High Resistance Meter.

Water content is determined in accordance with German Standard DIN 51777(%).

Weight Retained (%) after 7 Days at 136° C. (Wt. Ret.) is measured onspecimens of 1.25 inch diameter that are cut from 30 mil thick moldedplaques.

The wet insulation resistance is measured on wire samples with 14 AWGsolid copper conductor and 0.015 in. insulation thickness according toUL 83/2556. The sample lengths are 14 feet, with 10 feet in a coilimmersed in water and 2 feet on both ends acting as leads to the powersource. The samples are aged in a water bath at 75° C. and under 600 VAC for a period of up to 36 weeks. The insulation resistance is measuredwith 500 V DC applied for 60 seconds with a Quadtech 1868A megohmmeter.The first measurement is conducted after 6 hours of water immersion,with no voltage applied. All subsequent measurements are taken at aweekly frequency.

By way of example, and not by limitation, examples of the presentdisclosure are provided.

EXAMPLES A. Acetylated Castor Component Example 1 Acetylated Castor WaxSample (ACW1)—Preparation

Castor wax (110 g) and acetic anhydride (40 g) are charged in a 250mL-flask. The flask is fixed to a vacuum rotation evaporator and heatedto 100° C. until the wax is molten. The reaction is carried out at 120°C. over 4 hours at normal pressure. Vacuum of 800 to 100 mbar is used toremove acetic acid at a bath temperature of 115° C. A liquid product isobtained.

Example 2 Acetylated Castor Wax (ACW2)—Preparation

Castor wax (1 kg) is charged in a 2 L-flask. The flask is fixed withmechanical stirrer and common distillation glassware in a preheated bathof 100° C. Acetic anhydride (370 g) is added after melting of the wax.The temperature rises due to an exothermic reaction and is maintained at115° C. over 4 hours. Vacuum from 800 to 180 mbar is used to removeacetic acid at a bath temperature of 115° C. A liquid product isobtained.

Example 3 Acetylated Castor Oil Sample (ACO)—Preparation

Castor oil (110 g) and acetic anhydride (40 g) are charged in a 250mL-flask. The flask is fixed to a vacuum rotation evaporator, heated to120° C. and the temperature is maintained at 120° C. for 3 hours. Vacuumof 800 to 150 mbar is used to remove acetic acid at a bath temperatureof 120° C. A liquid product is obtained.

Example 4 Acetylated Castor Wax (ACW3)—Preparation

Castor wax (3700 g) is charged in a 5 L-reactor. The reactor is fixedwith mechanical stirrer and common distillation glassware and is heatedby an external bath to a temperature of 100° C. After melting the castorwax, acetic anhydride (1233 g) is added. Temperature falls to 84° C. andrises to 115° C. by the exothermic reaction. Temperature is maintainedat 115° C. (inside) over 8 hours. Vacuum from 800 to 150 mbar is used toremove acetic acid until the Acid Number is lower than 3 mg KOH/g. Aliquid product is obtained.

Example 4A Acetylated Castor Wax (ACW3A)—Preparation

Castor wax (3700 g) is melted over night at 105° C. and charged in a 5L-reactor. The reactor is fixed with mechanical stirrer and commondistillation glassware and is heated by an external bath to atemperature of 105° C. Acetic anhydride (1233 g) is added. Temperaturefalls to 88° C. and rises to 115° C. by the exothermic reaction.Temperature is maintained at 120° C. (inside) over 8 hours and at roomtemperature overnight. Vacuum from 800 to 150 mbar is used to removeresidual acetic acid at a bath temperature of 115° C. until the AcidNumber is 1.6 mg KOH/g. A liquid product is obtained.

Example 5 Acetylated castor oil sample (ACO)—Preparation

Castor oil (773 g) and acetic anhydride (266 g) are charged a 2 L-flask.The flask is fixed with mechanical stirrer and common distillationglassware in a preheated bath of 115° C. The temperature is maintainedat 115° C. over 6 hours. Vacuum from 800 to 150 mbar is used to removeacetic acid at a bath temperature of 115° C. A liquid product isobtained.

Table 2 below sets forth the properties of Examples 1-5, in comparisonwith comparative samples (commercially available acetylated derivativesof castor oil and castor wax). The plasticizers of Examples 1, 2 and 4(ACW) are substantially less viscous than comparative sample 3. Theplasticizers of Example 3 and 5 (ACO) have a lower hydroxyl number thancomparative sample 1. All plasticizers of Examples 1 to 5 exhibit lowervolatility (i.e., higher temperature of 5% mass loss), lower specificgravity, and a higher solution temperature than comparative sample 2.

TABLE 2 Ex 1 Ex 2 Ex. 3 Ex 4 Ex 4A Ex. 5 CS 1 CS 2 ACW1 ACW2 ACO ACW3ACW3A ACO FP-8 S-N-S CS 3 Property Yellow Yellow Yellow Yellow YellowYellow Yellow Clear Pari 8 App. Liq. Liq. Liq. Liq. Liq. Liq. Liq. Liq.Paste IV 3 3 75 4 4 75 76 4 max. 2 AN 1.5 1.0 3.6 2.4 1.6 1.9 1.2 1.51.8 OHN 0 0 0 0 0 0 5 0 9.4 Sol. Temp 197 190 190 194 194.5 189 190.5151 >200 5% Temp 335 322 330 324 266 328 Water 0.19 0.02 0.05 0.03 0.010.01 0.07 0.03 0.1 Visc. 25° C. 340 340 — 345 345 240 230 100 5390 40°C. 145 145 — 150 150 115 115 45 1310 Dens. 0.953 0.952 0.974 0.953 0.9520.966 0.964 0.999 0.955 5% Temp. = Temp. of 5% mass loss (° C.), TG/TGAAN = acid number (mg KOH/g) DIN 53402 App. = Appearance @ RT CS =Comparative sample Dens. = Density (@ 25 C.) DIN 51757 FP-8 =Flexricin ® P-8 (acetylated castor oil) (available from Vertellus) IV =Iodine value (g I₂/100 g) Deutsche Einheitsmethode DGF C-V 11a (53) orfrom technical data sheet OHN = hydroxyl number (mg KOH/g) DIN 53240Pari 8 = Paricin ® 8 (acetylated castor wax) (available from Vertellus)S-N-S = Grindsted ® Soft-N-Safe (acetylated monoglyceride ofhydrogenated castor oil (available from Danisco) Sol. Temp = SolutionTemperature (° C.) DIN 53408 Visc. = Viscosity (mPas) ASTM D445Brookfield 25° C., 40° C. Water = wt % water, DIN 51777

Table 3 sets forth other plasticizers and the abbreviation and sourcefor each.

TABLE 3 Abbreviation Name Trade Name and Source EPGD Epoxidizedpropylene Vikoflex ® 5075, Arkema glycol dioleate ESO Epoxidized soybeanoil PLAS-CHEK ® 775, Ferro DIDP diisodecyl phthalate TCI Japan DOPdioctyl phthalate TCI America DTDP Diisotridecyl phthalate ScientificPolymer Products TINTM triisononyl trimellitate Sigma-Aldrich, AmericaTOTM trioctyl trimellitate Sigma-Aldrich, America DINCH1,2-Cyclohexanedicarboxylic HEXAMOLL ® DINCH, acid, diisononyl esterBASF

B. Thermoplastic Compositions: Blends of PVC & Plasticizer Composition

Thermoplastic compositions composed of blends of polyvinylchloride (PVC)with various plasticizer compositions and additives are prepared asshown in Table 4 below.

TABLE 4 Thermoplastic Compositions Blend 1 Blend 2 Blend 3 Blend 4 Blend5 Blend 6 Blend 7 Blend 8 Blend 9 Blend 10 Blend 10A PVC 63.9 63.9 63.963.9 63.9 63.9 63.9 63.9 62.3 63.9 63.0 Plasticizer 23.8 23.8 23.8 23.8n/a (ESO is sole 27.3 27.3 27.3 30.0 27.3 27.3 (87)* (87)* (87)* (87)*plasticizer) (100)* (100)* (100)* (100)* (100)* (100)* CaCO3 6.4 n/a 3.2n/a n/a n/a n/a n/a n/a n/a n/a Polyfil ® 70 n/a 6.4 3.2 6.4 6.4 6.4 6.46.4 n/a n/a n/a Satintone ® n/a n/a n/a n/a n/a n/a n/a n/a 6.4 6.4 6.4SP-33 ESO 3.5 3.5 3.5 3.5 27.3 (present as (present in (present in(present as (present in (present as (13)* (13)* (13)* (13)* (100)*plasticizer) some some plasticizer) some plasticizer) formulationsformulations formulations as plasticizer) as plasticizer) asplasticizer) Mark ® 6797 2.1 2.1 2.1 2.1 2.1 2.1 n/a n/a n/a n/a n/aBaeropan ® — — — — — — 2.1 — — — — MC 9754 KA Mark ® 6776 2.1 — — — ACMBaeropan ® 1.0 — 3.0 MC 90249 KA Naftosafe ® 2.1 — EH-314 Irganox ® 0.30.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 1076 Baeropan ® MC 90249 KA =calcium-zinc heat stabilizer (Baerocher) Baeropan ® MC 9754 KA =calcium-zinc heat stabilizer (Baerlocher) CaCO₃ = Hubercarb ® Q1Tcalcium carbonate Irganox ® 1076 = hindered phenolic antioxidant (CibaChemicals) Mark ® 6797 = calcium-zinc stabilizer (Chemtura Corp.) Mark ®6776 ACM = barium-zinc stabilizer (Chemtura Corp.) Naftosafe ® EH-314 =calcium-zinc heat stabilizer (Chemson) Polyfil ® 70 = kaolin clay PVC =polyvinyl chloride homopolymer (OxyVinyls ® 240F) Satintone ® SP-33 =calcined clay Values = wt % based on total weight of composition *Wt %based on weight of total plasticizer

Thermoplastic Compositions 1, 2 and 5 (Blends 1, 2, and 5)

The following procedure is used to prepare the Blends 1, 2 and 5:

-   -   Weigh the individual ingredients and mix all in a container        using a spatula    -   Use “40 cm³” Brabender mixing bowl with conventional rotors to        make batches of each formulation at 40 rpm setting    -   Do not purge mixing bowl with nitrogen    -   Add mixture of PVC and other ingredients, and mix at 175° C. for        5 minutes

The blend compositions from the mixing bowl are compression molded into30 mil thick plaques at 175° C. for 5 minutes for testing of allproperties except volume resistivity. Volume resistivity is measured onspecimens cut from 40 mil thick molded plaques.

Thermoplastic Compositions 3 and 6 (Blends 3 and 6)

The following procedure is used to prepare Blends 3 and 6:

-   -   Preheat plasticizers (and epoxidized soybean oil if applicable)        to 60° C. for at least 30 minutes and shake before use    -   Weigh the individual solid ingredients and mix all in a        container using a spatula    -   Make ‘dry blends’ by soaking plasticizer into PVC powder, as        follows    -   Use “40 cm³” Brabender mixing bowl with sigma blades at 80° C.        to make batches of each formulation at 40 rpm setting    -   Do not purge mixing bowl with nitrogen    -   After 2 min warm-up, add mixture of PVC powder, filler, Mark®        6797 and Irganox® 1076 and mix for 5 minutes    -   Add plasticizer and mix for 15 minutes    -   Stop and remove “dry blend”    -   The ‘dry blends’ are subsequently melt mixed using the following        procedure:    -   (a) Mix in a “40 cm³” Brabender mixing bowl with conventional        rotors at 40 rpm setting    -   (b) Do not purge mixing bowl with nitrogen    -   (c) Add ‘dry blend’, and mix at 175° C. for 5 minutes

The blend compositions are removed from the mixing bowl and arecompression molded at 175° C. for 5 minutes. Specimens are cut from 30mil thick molded plaques for testing of all properties except volumeresistivity. Volume resistivity is measured on specimens cut from 40 milthick molded plaques.

Thermoplastic Compositions 4, 7 and 8 (Blends 4, 7 and 8)

The following procedure is used to prepare Blends 4, 7 and 8:

-   -   Preheat plasticizer (and epoxidized soybean oil if applicable)        to 60° C. for minimum 30 minutes, mix and shake before use    -   Weigh the individual solid ingredients and mix all in a        container using a spatula    -   Use a Henschel mixer to mix 1 kg of ‘dry blend’ at a set        temperature of 80° C. and 1800 rpm, by first fluxing the solids        mixture and then adding the plasticizer, recording time for        plasticizer sorption to be completed.    -   The ‘dry blend’ is melt mixed using a conical twin screw        extruder (25:1 L/D) at 45 rpm and set temperature profile of        zone 1=160° C., zone 2=165° C., zone 3=170° C., die=175° C.    -   The extruded strands are subsequently air cooled and pelletized.

The pellets are compression molded at 175° C. for 5 minutes. Specimensare cut from 30 mil molded plaques for testing of all properties exceptvolume resistivity. Volume resistivity is measured on specimens cut from40 mil thick molded plaques. The pellets from Blend 4 and Blend 8 arealso used to fabricate wire/cable by coating onto a 0.064 inch (14 AWG)solid copper conductor using 25:1 single-screw extruder at settemperatures of 160° C., 165° C.; 170° C.; 175° C. The outside diameterof the coated conductor is approximately 0.094 inch (approximately 0.015inch thick wall). Die pressures during wire extrusion are noted.

Thermoplastic Composition 9 (Blend 9)

The following procedure is used to prepare Blend 9:

-   -   Preheat Paricin® 8 and epoxidized soybean oil to 60° C. for at        least 60 minutes, shake and make a 25/75 wt % Paricin® 8/ESO        mixture (plasticizer composition)    -   Make “solids mixture” by mixing all ingredients (except        plasticizer and clay filler) in a container using a spatula    -   Make ‘dry blends’ by soaking plasticizer into PVC powder, as        follows    -   Use “40 cm³” Brabender mixing bowl with sigma blades at 90° C.        to make batches of each formulation at 40 rpm setting    -   Do not purge mixing bowl with nitrogen    -   After 2 min warm-up, add “solids mixture” and mix for 30 seconds    -   Add plasticizer and mix for 6 minutes    -   Add filler (clay) and mix for 60 seconds    -   Stop and remove “dry blend”    -   The ‘dry blend’ is subsequently melt mixed using the following        procedure:    -   (a) Mix in a “40 cm³” Brabender mixing bowl with cam rotors at        40 rpm setting    -   (b) Do not purge mixing bowl with nitrogen    -   (c) Add ‘dry blend’, and mix at 180° C. for 2 minutes

The blend composition is removed from the mixing bowl and is compressionmolded at 180° C. for 5 minutes. Specimens are cut from 30 mil thickmolded plaques for testing of all properties except volume resistivityand Shore hardness. Volume resistivity is measured on specimens cut from40 mil thick molded plaques. Shore hardness is measured on moldedspecimens of 250 mil thickness.

Thermoplastic Composition 10 (Blend 10)

The following procedure is used to prepare Blend 10:

-   -   Preheat ACW, ESO, S-N-S, TOTM and DINCH to 60° C. for at least        60 minutes. Shake and make the 50/50 wt % ACW/ESO, ACW/S-N-S,        ACW/TOTM, ACW/DINCH mixtures (plasticizer compositions)    -   Make “solids mixture” by mixing all ingredients (except        plasticizer and clay filler) in a container using a spatula    -   Make ‘dry blends’ by soaking plasticizer into PVC powder, as        follows    -   Use “40 cm³” Brabender mixing bowl with sigma blades at 80° C.        to make batches of each formulation at 40 rpm setting    -   Do not purge mixing bowl with nitrogen    -   After 2 min warm-up, add “solids mixture” and mix for 30 seconds    -   Add plasticizer and mix for 2 minutes    -   Add filler (clay) and mix for 60 seconds    -   Stop and remove “dry blend”    -   The ‘dry blend’ is subsequently melt mixed using the following        procedure:    -   (a) Mix in a “40 cm³” Brabender mixing bowl with cam rotors at        40 rpm setting    -   (b) Do not purge mixing bowl with nitrogen    -   (c) Add ‘dry blend’, and mix at 175° C. for 2 minutes

The blend composition is removed from the mixing bowl and is compressionmolded at 175° C. for 5 minutes. Specimens are cut from 30 mil thickmolded plaques for testing of all properties except volume resistivity.Volume resistivity is measured on specimens cut from 40 mil thick moldedplaques.

Thermoplastic Composition 10A (Blend 10A)

The following procedure is used to prepare Blend 10A:

-   -   Preheat the plasticizer to 60° C. for at least 60 minutes and        shake before use    -   Weigh out the individual ingredients    -   First make ‘dry blend’ by soaking plasticizer into PVC powder,        and then make melt mixture    -   The following procedure is used for preparations of the ‘dry        blend’:    -   (a) Make “solids mixture” by mixing everything (except        plasticizer and filler) in a container using spatula.    -   (b) Use a Henschel type high-intensity mixer to prepare 3 kg of        ‘dry blend’ at a set temperature of 90° C. and 1800 rpm, by        first fluxing the solids mixture for 60 seconds, then adding and        mixing the plasticizer over a period of 360 seconds (6 minutes),        and finally adding the clay and mixing for additional 90        seconds.    -   (c) Stop and remove “dry blend”.    -   The ‘dry blend’ is subsequently melt mixed using a conical twin        screw extruder (25:1 L/D) at 45 rpm and set temperature profile        of zone 1=170° C., zone 2=175° C., zone 3=180° C., die=185° C.        The extruded strands are subsequently air cooled and pelletized.

The pellets are compression molded at 180° C. for 5 minutes. Specimensare cut from 30 mil molded plaques for testing of all properties exceptvolume resistivity and Shore hardness. Volume resistivity is measured onspecimens cut from 40 mil thick molded plaques. Shore hardness ismeasured on molded specimens of 250 mil thickness. The pellets are alsoused to fabricate wire/cable by coating onto a 0.064 inch (14 AWG) solidcopper conductor using 25:1 single-screw extruder at 40 rpm and settemperatures of 170° C., 175° C.; 180° C.; 185° C. The outside diameterof the coated conductor is approximately 0.094 inch (i.e., approximately0.015 inch thick insulation). Die pressures during wire extrusion arenoted. Wet insulation resistance at 75° C. of the wire is measured.

Table 5 provides properties for the various thermoplastic compositions.

TABLE 5 Blend # Plasticizer† Shore (A) Shore (D) Tg G’ −20° C. TS(Unaged) TSR 113° C. TSR 136° C. TE (Unaged) TER 113° C. TER 136° C. WtRet. Spew 113° C. Spew 136° C. Vol Res 5% Temp  1 Ex 1 (87) 95.9 ± 0.255.2 7.70E+08 2844 ± 65  90 ± 3  93 ± 3 268 ± 0  86 ± 1 76 ± 4  n/a4.13E+11 n/a ESO (13)  1 DIDP (87) 91.1 ± 0.3 28.1 9.51E+08 2947 ± 288 114 ± 30  171 ± 16  243 ± 32  97 ± 43 18 ± 16 n/a 7.54E+12 n/a ESO (13) 1 TINTM (87) 91.3 ± 0.4 30.6 1.10E+09 2732 ± 319 110 ± 3  107 ± 13  229± 38 111 ± 7 91 ± 17 n/a 7.04E+12 n/a ESO (13)  2 Ex 1 (87) 93.8 ± 0.958.8 7.82E+08 2083 ± 73 105 ± 2 103 ± 3  87 ± 8  66 ± 5 93 ± 11 97.35.56E+11 n/a ESO (13)  2 TOTM (87) 87.5 ± 1.3 41.4 n/a 2441 ± 34  96 ± 8116 ± 5 115 ± 4  88 ± 11 75 ± 7  96.7 3.24E+13 n/a ESO (13)  2 Pari 8(87) 90.8 ± 1.0 60.5 9.14E+08 1832 ± 30 108 ± 5 110 ± 2  55 ± 2  36 ± 578 ± 12 96.1 6.53E+11 n/a ESO (13)  2 S-N-S (87) 89.3 ± 0.2 25.79.71E+08 2340 ± 3 112 ± 3  177 ± 32  141 ± 13  89 ± 11 4 ± 3 91.54.63E+11 n/a ESO (13)  3 Ex 1 (87) 96.3 ± 0.5 60.1 8.42E+08 3277 ± 162105 ± 5 102 ± 3 234 ± 9  95 ± 3 77 ± 10 98.1 1.35E+12 n/a ESO (13)  3 Ex2 (87) 95.0 ± 0.8 63.0 8.38E+08 3183 ± 149  96 ± 6 100 ± 4  225 ± 14  98± 8 79 ± 16 98.4 1.52E+12 n/a ESO (13)  3 TOTM (87) 93.3 ± 0.3 39.81.39E+09 3925 ± 158  83 ± 24 108 ± 4 282 ± 5  73 ± 37 86 ± 1  97.36.87E+13 n/a ESO (13)  4 Ex 2 (87) 97.3 ± 0.5 59.6 9.20E+08 3709 ± 86 89 ± 10  80 ± 11  234 ± 31  76 ± 33 79 ± 27 98.7 8.75E+11 280 ESO (13) 4 TOTM (87) 97.4 ± 0.2 41.0 1.48E+09 4136 ± 69  90 ± 2  86 ± 2  232 ±98  113 ± 69 96 ± 48 97.5 6.47E+13 265 ESO (13)  1 Ex 3 (87) 96.5 ± 0.355.4 8.47E+08 2332 ± 37 103 ± 3 101 ± 1 134 ± 5  99 ± 1 66 ± 4  n/a1.17E+12 ESO (13)  1 DIDP (87) 93.1 ± 0.3 39.4 1.03E+09 2308 ± 10  118 ±23  249 ± 10 149 ± 2  37 ± 16 2 ± 0 n/a 8.63E+12 ESO (13)  1 TOTM (87)95.0 ± 0.3 40.5 1.24E+09 2356 ± 47 105 ± 3 108 ± 2 136 ± 4 101 ± 5 82 ±2  n/a 4.61E+13 ESO (13)  2 Ex 3 (87) 93.3 ± 0.7 54.3 7.71E+08 2172 ± 30 98 ± 3  189 ± 13 102 ± 3  82 ± 3 6 ± 2 94.7 5.43E+11 ESO (13)  2 FP-8(87) 89.9 ± 0.5 55.5 8.33E+08 2287 ± 146  94 ± 2 150 ± 3  86 ± 6  83 ±11 19 ± 17 95.7 5.69E+11 ESO (13)  5 ESO (100) 92.9 ± 0.1 32.7 1.26E+092464 ± 112 108 ± 4  233 ± 20 116 ± 2  98 ± 4 3 ± 0 96.1 n/a n/a 7.72E+12 6 Ex 2 (87) 96.1 ± 0.5 61.7 1.13E+09 3104 ± 391  102 ± 24  99 ± 12  184± 48  83 ± 46 68 ± 19 97.9 n/a n/a 3.51E+12 ESO (13) EPGD (0)  6 Ext(43.5) 95.6 ± 0.2 44.2 1.24E+09 3723 ± 98  91 ± 12  96 ± 1 264 ± 12  81± 21 49 ± 5 96.3 n/a n/a 2.82E+12 ESO (13) EPGD (43.5)  7 Ex 4 (87) 96.1± 0.2 64.5 6.97E+08 2024 ± 302  115 ± 23  101 ± 19 105 ± 44  90 ± 59 60± 18 98.1 Heavy Moderate 1.16E+14 ESO (13)  7 Ex 4 (50) 94.5 ± 1.6 48.11.12E+09 3579 ± 42  107 ± 13  95 ± 4 253 ± 6  91 ± 7 81 ± 8 99.7 SlightSlight 3.86E+14 ESO (50)  7 TOTM (50) 94.8 ± 0.2 49.7 1.12E+09 3162 ±435  110 ± 26  120 ± 31 184 ± 46  115 ± 56 82 ± 57 94.7 None None1.34E+15 DTDP (50)  7 Ex 4 (100) 97.0 ± 0.3 73.7 5.69E+08 1591 ± 130 103± 8  126 ± 16  56 ± 9  32 ± 17 100 ± 47  98.2 Heavy Moderate 1.17E+14  8TOTM (50) 94.5 ± 0.6 45.0 1.16E+09 4152 ± 307  98 ± 8 105 ± 6 273 ± 4 108 ± 10 87 ± 10 94.8 n/a n/a 1.21E+16 DTDP (50)  8 Ex 4 (50) 94.2 ±0.3 46.9 9.75E+08 4042 ± 324 104 ± 8  97 ± 7  275 ± 12 119 ± 3 103 ± 4  99.8 n/a n/a 3.92E+15 ESO (50)  9 Pari 8 (25) n/a 35.3 ± 1.0 n/a n/a3621 ± 30  98 ± 1  99 ± 2 282 ± 5 101 ± 1 86 ± 1  99.7 None None4.95E+15 ESO (75) 10 Ex 4 (50) 94.7 ± 1.2 48.2 ± 0.6 n/a n/a 3848 ± 83104 ± 7 100 ± 3 256 ± 8  96 ± 13 43 ± 21 99.4 Slight Moderate 5.88E+15ESO (50) 10 Ex 4 (50) 92.0 ± 0.8 42.2 ± 0.3 n/a n/a 3584 ± 208 114 ± 5 105 ± 13  258 ± 22 103 ± 7 67 ± 18 94.7 None None 7.78E+15 S-N-S (50)10 Ex 4 (50) 94.9 ± 0.8 47.6 ± 0.4 n/a n/a 3729 ± 172 110 ± 5 106 ± 4 224 ± 21  116 ± 14 87 ± 17 96.1 None None 9.73E+15 TOTM (50) 10 Ex 4(50) 94.2 ± 0.3 45.6 ± 0.7 n/a n/a 3968 ± 155 119 ± 6 121 ± 8  274 ± 10 78 ± 5 65 ± 7  85.6 None None 9.59E+15 DINCH (50) 10A Ex 4A (50) n/a45.0 ± 0.5 n/a n/a 3626 ± 211  99 ± 5  89 ± 8  251 ± 30  92 ± 5 51 ± 0 99.4 n/a n/a 7.65E+15 ESO (50) † = Weight percent for plasticizercomponents is shown in parenthesis. Weight percent is based on totalweight of the plasticizer

TABLE 6 Time to Make Dry Blends Blend # Plasticizer† Time to Make DryBlend (minutes) 4 Ex 2 (87) 5.0 ESO (13) 4 TOTM (87) 4.5 ESO (13) 7 Ex 4(87) 3.6 ESO (13) 7 Ex 4 (50) 1.8 ESO (50) 7 TOTM (50) 3.9 DTDP (50) 7Ex 4 (100) Still wet after 8 minutes 8 TOTM (50) 5.8 DTDP (50) 8 Ex 4(50) 3.3 ESO (50) †= Weight percent for plasticizer components is shownin parenthesis. Weight percent is based on total weight of theplasticizer

Plasticizer composition containing 50/50 weight percent Ex 4/ESO soaksinto PVC more quickly than do the comparative plasticizers (50/50 weightpercent TOTM/DTDP and 50/50 weight percent TOTM/ESO), as evident fromTable 6. Increasing the amount of ESO in the plasticizer compositionalso contributes to a shorter soak time.

FIG. 1 is a plot showing the shear dependent viscosity at 200° C. of anembodiment of the present composition (87/13 wt % Example 2/ESO in Blend4) compared to the plasticizer 87/13 wt % TOTM/ESO (in Blend 4). FIG. 1illustrates that the present composition exhibits greater shear thinningthan a comparative composition containing TOTM plasticizer.

TABLE 7 Volume Resistivity after Aging in 90° C. Water Bath VolumeResistivity (Ohm cm) at 23° C. Blend # Plasticizer† 1 day 3 days 7 days7 Ex 4 (87) 2.35E+11 3.36E+13 1.68E+12 ESO (13) 7 Ex 4 (50) 2.01E+142.01E+14 1.71E+14 ESO (50) 7 TOTM (50) 2.68E+14 2.68E+14 2.09E+14 DTDP(50) 7 Ex 4 (100) 5.85E+10 1.01E+09 1.52E+08 8 TOTM (50) 2.45E+156.49E+15 n/a DTDP (50) 8 Ex 4 (50) 1.90E+15 2.18E+15 n/a ESO (50)  10AEx 4A (50) 3.18E+15 2.20E+15 1.10E+15 ESO (50) †= Weight percent forplasticizer components is shown in parenthesis. Weight percent is basedon total weight of the plasticizer

Increasing the amount of ESO in the exemplary plasticizers, results in ahigher volume resistivity compared to the comparative samples,especially after aging in the 90° C. water bath (Table 7).

TABLE 8 Results from Wire Extrusion Die Surface TS TE Blend ExtruderPressure Smoothness (Unaged)- TSR (Unaged)- TER # Plasticizer† RPM (psi)(μ in) psi 136° C. % ° C.  4 Ex 2 (87) 14 940 156 ± 79  1771 ± 5  106 ±3 40 ± 2  93 ± 7 ESO (13)  4 Ex 2 (87) 40 1640 40 ± 12 2076 ± 8  133 ± 283 ± 2  92 ± 3 ESO (13)  4 TOTM (87) 14 1820 82 ± 17 2368 ± 27 143 ± 263 ± 5 122 ± 8 ESO (13)  8 TOTM (50) 40 2470 71 ± 20 2234 ± 15 163 ± 146 ± 4  122 ± 56 DTDP (50)  8 Ex 4 (50) 40 2500 24 ± 8  2003 ± 3  124 ±4 63 ± 6  118 ± 16 ESO (50) 10A Ex 4A (50) 40 1640 40 ± 17 2461 ± 34 130± 4 82 ± 9  84 ± 15 ESO (50) † = Weight percent for plasticizercomponents is shown in parenthesis. Weight percent is based on totalweight of the plasticizer

TABLE 8A Wet Insulation Resistance (Megaohms/1000 ft) at 75° C. ofExtruded Wire Days in Water Blend # Plasticizer† 0.25 7 14 21 28 35 4249 56 63 70 77 84 91 98 105 10A Ex 4A (50) 0.457 0.716 0.589 0.569 0.4050.556 0.550 0.525 0.479 0.504 0.505 0.458 0.389 0.412 0.400 0.428 ESO(50) Days in Water Blend # Plasticizer† 112 119 126 133 140 146 153 160167 174 181 188 195 202 209 10A Ex 4A (50) 0.420 0.424 0.416 0.051 1.4100.422 0.424 0.431 0.419 0.373 0.385 0.381 0.385 0.383 0.392 ESO (50) † =Weight percent for p asticizer components is shown in parenthesis.Weight percent is based on total weight of the plasticizer

Compared to the comparative samples, the exemplary plasticizerscontaining ESO result in (1) smooth cable coating with (2) excellentretention of tensile properties after heat aging at 136° C., as evidentfrom Table 8. Furthermore, exemplary plasticizer containing ESO resultsin excellent electrical properties (Table 8A). In particular, thelong-term wet insulation resistance of the wire is excellent, well abovethe minimum pass requirement of 0.115 Megaohms/1000 ft and passing thestability criteria of less than 2% decrease per week in insulationresistance after 24 weeks.

C. Effect of Castor Wax Grade on Acetylated Castor Component Examples 6to 10 Effect of Castor Wax Grade on Color and Insolubles Content ofAcetylated Castor Wax at Room Temperature

Acetylation is done on five different grades of castor wax (CW6, CW7,CW8, CW9, CW10). The castor wax materials are obtained from differentsuppliers, and used in the acetylation reaction as received. 75 g ofeach castor wax sample is put into a 250 mL three-necked flask equippedwith a stirring bar, a condenser, a thermometer and an additionalfunnel. The mixture is covered under nitrogen. The solid startingmaterial is melted at 85-95° C. To this mixture, 25 g of aceticanhydride is slowly added via additional funnel at 100° C. The mixtureis kept at this temperature for 17 hours. The resulting acetylatedmixture is cooled to 75° C. The condenser is replaced by distillationhead (short path). The excess of acetic anhydride and by-product aceticacid are removed under vacuum (using a vacuum pump, ˜10-30 mm Hg). Thereaction mixture is heated slowly to 100° C. Total distillation time is5-6 hours. The products, acetylated castor wax samples ACW6, ACW7, ACW8,ACW9, ACW10, are cooled to room temperature and discharged from theflask when the distillation is completed. The results are summarized inTable 9. Color is measured using Color Quest XE from HunterLab. Acidnumber is measured using 0.1 N KOH/MeOH, 50/50 xylenes/isopropanol, andphenolphthalein as indicator. Table 9 shows that the starting castor waxmaterial plays a very important role in product color and formation ofinsolubles (haze). The products ACW6-ACW10 exhibit differences in termsof color and haze formation based on the supplier/grade of the startingcastor wax.

TABLE 9 Effect of castor wax grade on color and haze (insolublescontent) of ACW Acid number of Starting Color Acid Haze Castor Wax(APHA-20 number (Insolubles) Material (mg KOH/g) mm) (mg KOH/g) Formed @22° C. ACW6 1.2 288 0.3 None ACW7 2.2 390 0.5 High ACW8 1.5 409 0.4 NoneACW9 1.9 741 0.4 Low ACW10 1.5 279 0.4 None

D. Purification of Castor Wax by Re-Crystallization to Decrease Colorand Insolubles Content of Acetylated Castor Component Examples 11 to 13Purification of Castor Wax, by Re-Crystallization from Ethyl Acetate orAcetone, as a Means of Decreasing Color and Insolubles Content ofAcetylated Castor Wax (ACW11, ACW12, ACW13)

The starting material (castor wax) is recrystallized from ethyl acetateor acetone before use in the acetylation reaction. Re-crystallization ofthe castor wax improves the color of the acetylated castor wax andresults in lighter color. ACW11 and ACW12 have a lower APHA value thannon-recrystallized ACW6. Similarly, ACW13 has a lower APHA value thannon-recrystallized ACW7. The results are shown in Table 10.

TABLE 10 Recrystallization of castor wax starting material as a way todecrease color and insolubles content of ACW Acetylated Color (APHA-Acid number (mg Haze (Insolubles) Starting Material (Castor Wax)Material 20 mm) KOH/g) Formation @ 22° C. CW6--As received ACW6 288 0.3None CW6 recrystallized 1x from acetone ACW11 253 Not Measured None CW6recrystallized 2x from acetone ACW12 247 Not Measured None CW7--Asreceived ACW7 390 0.5 High CW7 recrystallized 1x from ethyl acetateACW13 286 Not Measured Medium

It is specifically intended that the present disclosure not be limitedto the embodiments and illustrations contained herein, but includemodified forms of those embodiments including portions of theembodiments and combinations of elements of different embodiments ascome within the scope of the following claims.

1-10. (canceled)
 11. A composition comprising: a first plasticizercomprising an acetylated castor component comprising triglycerideshaving fatty acid chains of 4 to 22 carbon atoms; and a secondplasticizer comprising an epoxidized fatty acid ester.
 12. Thecomposition of claim 1, wherein the acetylated castor component has ahydroxyl number from 0 to less than
 5. 13. The composition of claim 1,wherein the acetylated castor component has a hydroxyl number from 0 toless than
 2. 14. The composition of claim 1 wherein the acetylatedcastor component is selected from the group consisting of acetylatedcastor oil, acetylated castor wax, and combinations thereof.
 15. Thecomposition of claim 14, wherein the acetylated castor component is anacetylated castor oil having an iodine number from about 40 g I₂/100 gto about 90 g I₂/100 g.
 16. The composition of claim 15, wherein theacetylated castor oil has a viscosity from about 50 mPa s as measured inaccordance with ASTM D445 at 25° C.
 17. The composition of claim 14,wherein the acetylated castor component is an acetylated castor waxhaving a viscosity less than 2000 m Pa s as measured in accordance withASTM D445 at 25° C.
 18. The composition of claim 17, wherein theacetylated castor wax has an iodine number of 0 to less than 40 g I₂/100g.
 19. The composition of claim 11, wherein the acetylated castorcomponent comprises 40-95 wt % glyceryl trihydroxystearate.
 20. Thecomposition of claim 11, wherein the acetylated castor component has anacid number from about 0 mg KOH/g to about 8 mg KOH/g.
 21. Thecomposition of claim 11, wherein the epoxidized fatty acid ester isepoxidized soybean oil.
 22. The composition of claim 11 comprising lessthan 70 wt % of the acetylated castor component.
 23. The composition ofclaim 11 having a solution temperature from 140° C. to 200° C.
 24. Apolymeric composition comprising: a polymeric resin; and a plasticizercomposition comprising an acetylated castor component having a hydroxylnumber from 0 to less than 5 and an epoxidized fatty acid ester.
 25. Thepolymeric composition of claim 24, wherein the polymeric resin comprisesa vinyl chloride resin.
 26. The polymeric composition of claim 24,wherein the composition is a plaque having a tensile elongationretention after 168 hours heat aging at 113° C. of greater than 50%. 27.The polymeric composition of claim 24, wherein the composition is aplaque having a tensile strength retention greater than about 70% after168 hours heat aging at 113° C.